Printing inks and lacquers containing polyolefin waxes

ABSTRACT

Printing inks and paints comprising a polyolefin wax component prepared from one or more olefins by catalysis using a single-site catalyst based on a complex of a transition metal from groups 5 to 8 of the Periodic System of the Elements, which comprises not more than one cyclopentadienyl system per transition metal.

The present invention relates to printing inks and paints comprising apolyolefin wax component prepared from one or more olefins by catalysisusing a single-site catalyst based on a complex of a transition metalfrom groups 5 to 8 of the Periodic System of the Elements, whichcomprises not more than one cyclopentadienyl system per transitionmetal. The present invention further relates to micronized particles ofpolyolefin waxes for use in the printing inks and paints of theinvention, to a process for preparing printing inks and paints using themicronized polyolefin wax particles of the invention, and to a method ofprinting paper or cardboard using the printing inks of the invention.

Paints and printing inks are composed of a plurality of constituents.

The four principal constituents of printing inks are:

-   -   colorants, usually synthetic organic or inorganic pigments;        examples are        -   inorganic pigments such as TiO₂, iron blue pigments or iron            oxide pigments;        -   metal pigments such as bronzes, an example being aluminum            powder (“silver bronze”), brass powder (“gold bronze”) or            copper powder (“copper bronze”);        -   interference pigments, e.g., mother of pearl, pearl lustre;        -   pigmentary carbon black;        -   organic azo pigments, isoindoline pigments, phthalocyanine            pigments or luminescent pigments;    -   fillers, examples being calcium carbonate, aluminum oxide        hydrate, barium sulfate, silica, aluminum silicate (kaolin) or        magnesium silicate (talc);    -   binders, selected from fatty, oxidatively drying or nondrying        oils and—prepared from them—alkyd resins or solutions of resins;    -   solvents, such as water.

Furthermore, auxiliaries are incorporated as secondary constituents,examples being waxes, fatty acid amides, plasticizers, siccatives, anddrying retardants.

Toners for copiers may be defined as special printing inks, comprisingwaxes not as a secondary constituent but instead as a principalcomponent.

The effects of waxes in printing inks and paints are several:

-   -   they increase the abrasion, scratch and scuff resistance, i.e.,        the mechanical properties of printed products;    -   in liquid paints, they act as rheological additives; i.e., they        may support the alignment of pigments, especially effect        pigments, and may control the settling behavior of pigments and        fillers;    -   they may hydrophobicize the surfaces and so enhance the dirt        repellence;    -   they increase the lubricity of the printed surfaces and thus the        mechanical stability; for example, they reduce the formation of        metal marking tracks;    -   they increase the thermal load-bearing capacity; they can be        used to achieve dulling effects, by means of which it is        possible to improve, for example, the readability of printed        products even-under adverse light conditions (mirror effects).

So that waxes have the optimum morphology for paints and printing inks,they are preferably micronized, i.e., brought to the correct morphologyby grinding, spraying or (in the case of nonpolyethylene waxes) by beadpolymerization, by means of the chosen polymerization technique.Micronized waxes are understood, accordingly, to be wax powders having amaximum particle diameter of 30 μm.

It is important for the waxes used to possess a certain floatingcapacity, since this is prerequisite for optimum formation of slip,release and protective coats.

It is also a function of the waxes used to prevent the formation oflarge pigment agglomerates during the formulation process. Moreover, itis desirable to separate any agglomerated pigments formed beforehand andto split them into what are known as the primary particles. Finally, theprimary particles should also remain separate after the formulationprocess and should not undergo reaggregation on cooling.

To this end, a number of requirements are imposed on the wax. One ofthese requirements concerns the viscosity of the melt. The meltviscosity should be as low as possible so that during the formulation,which usually takes place by mixing at a temperature above the meltingtemperature of the wax, the melted wax is able to penetrate effectivelythrough the cavities within the pigment agglomerates. As a result of theshear forces exerted in this way, the splitting of the agglomerates intothe primary particles takes place more readily.

The wetting ability of the waxes should also be good.

In principle, natural and synthetic waxes may be used. The most suitablewaxes are polyolefin waxes. These may be obtained either by free-radicalpolymerization of ethylene by the high pressure process (cf. Ullmann'sEncyclopädie der technischen Chemie, 4th Edition, entry: Waxes, Vol. 24,p. 36 ff., Thieme Verlag Stuttgart, 1977) or by Ziegler-Nattapolymerization of ethylene or propylene (DE-A 15 20 914, EP-A 584 586).These methods allow polyolefin waxes to be obtained having a broadmolecular weight distribution and irregular incorporation of comonomers.The low molecular mass fractions which are present in these productslead in most cases to reduced hardness of the finished paints orprinting inks.

EP-A 890 619 discloses the use of waxes, preferably polyethylene waxes,obtained by metallocene catalysis. They improve the hardness of theprinting inks and paints prepared using them. For practical purposes,however, a further improvement is desirable. It is an object of thepresent invention to provide such an improvement.

We have found that this object is achieved in that waxes prepared withthe aid of a complex of the formula I a to c are especially suitable asadditives in printing inks and paints.

Waxes preparable with the aid of such single-site catalysts of atransition metal from groups 5 to 8 of the Periodic System whichcomprise not more than one cyclopentadienyl system per transition metalatom are known per se. The transition metal complexes required for thispurpose comprise compounds of the formula I a to c.

In formula I a

the variables are defined as follows:

-   M is an element from the group consisting of V, Nb, Ta, Cr, Mo, W,    Mn, Fe in oxidation state +3; preferably V, Cr or Mo, and with    particular preference Cr;-   X¹, X² are selected from    -   halogen such as fluorine, chlorine, bromine or iodine, chlorine        and bromine being particularly preferred;    -   trifluoroacetate,    -   BF₄ ⁻, PF₆ ⁻ or SbF₆ ⁻,    -   C₁-C₁₈ alkyl such as methyl, ethyl, n-propyl, iso-propyl,        n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl,        sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl,        iso-hexyl, sec-hexyl, n-heptyl, iso-heptyl, n-octyl, n-nonyl,        n-decyl, and n-dodecyl; preferably C₁-C₆ alkyl such as methyl,        ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl,        tert-butyl, n-pentyl, iso-pentyl, sec-pentyl, neo-pentyl,        1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl,        with particular preference C₁-C₄ alkyl such as methyl, ethyl,        n-propyl and n-butyl;    -   C₃-C₁₂ cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl,        cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl,        cycloundecyl and cyclododecyl; cyclopentyl, cyclohexyl and        cycloheptyl are preferred,    -   C₇ to C₂₀ aralkyl, preferably C₇ to C₁₂ phenylalkyl such as        benzyl, 1-phenethyl, 2-phenethyl, 1-phenylpropyl,        2-phenylpropyl, 3-phenylpropyl, 1-phenylbutyl, 2-phenylbutyl,        3-phenylbutyl and 4-phenylbutyl, with particular preference        benzyl,    -   C₆-C₁₄ aryl such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl,        2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl,        3-phenanthryl, 4-phenanthryl and 9-phenanthryl, preferably        phenyl, 1-naphthyl and 2-naphthyl, with particular preference        phenyl;    -   C₁-C₁₂ alkoxy, preferably C₁-C₆ alkoxy such as methoxy, ethoxy,        n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy,        tert-butoxy, n-pentoxy, iso-pentoxy, n-hexoxy and iso-hexoxy,        with particular preference methoxy, ethoxy, n-propoxy and        n-butoxy, or    -   NR⁸R⁹, where R⁸ and R⁹ independently of one another are selected        from hydrogen, C₁-C₁₂ alkyl, C₂-C₁₂ alkenyl and C₆-C₁₄ aryl,        which are able to form a saturated or unsaturated 5- to        10-membered ring; preference is given to the dimethylamino, the        diethylamino, the diisopropylamino, the methylphenylamino and        the diphenylamino groups. Examples of amino groups containing        saturated rings are the N-piperidyl group and the N-pyrrolidinyl        group; examples of amino groups containing unsaturated rings are        the N-pyrryl group, the N-indolyl group and the N-carbazolyl        group.

Preferably, X¹ and X² are identical; with very particular preference, X¹and X² are chlorine.

-   -   R¹ to R⁶ independently of one another are    -   hydrogen,    -   halogen such as fluorine, chlorine, bromine or iodine,        preference being given to chlorine and bromine;    -   C₁-C₁₈ alkyl such as methyl, ethyl, n-propyl, iso-propyl,        n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl,        sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl,        iso-hexyl, sec-hexyl, n-heptyl, iso-heptyl, n-octyl, n-nonyl,        n-Decyl, and n-dodecyl; preferably C₁-C₆ alkyl such as methyl,        ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl,        tert-butyl, n-pentyl, iso-pentyl, sec-pentyl, neo-pentyl,        1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl,        with particular preference C₁-C₄ alkyl such as methyl, ethyl,        n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and        tert-butyl,    -   C₁-C₁₂ alkyl substituted one or more times by donor atoms,        examples being noncyclic or cyclic ethers, alcohols, ketals,        thioethers or amines; specific examples are methoxymethyl,        ethoxymethyl, ethoxyethyl, β-hydroxyethyl, ω-ethoxypropyl,        (2-ethylhexyloxy)propylidene, methoxyethoxypropylidene or        ω-dimethylaminopropyl;    -   mono- or polyhalogenated C₁-C₁₂ alkyl groups such as        fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl,        dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl,        tribromomethyl, pentafluoroethyl, perfluoropropyl and        perfluorobutyl, particular preference being given to        fluoromethyl, difluoromethyl, trifluoromethyl and        perfluorobutyl;    -   C₂-C₁₂ alkenyl, preferably C₂ to ω-C₈ alkenyl such as vinyl,        allyl, but-3-en-1-yl, ω-pentenyl, ω-hexenyl, ω-heptenyl, and        ω-octenyl;    -   C₃-C₁₂ cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl,        cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl,        cycloundecyl and cyclododecyl; preference is given to        cyclopentyl, cyclohexyl and cycloheptyl;    -   C₇ to C₂₀ aralkyl, preferably C₇ to C₁₂ phenylalkyl such as        benzyl, 1-phenethyl, 2-phenethyl, 1-phenylpropyl,        2-phenylpropyl, 3-phenylpropyl, 1-phenylbutyl, 2-phenylbutyl,        3-phenylbutyl and 4-phenylbutyl, with particular preference        benzyl,    -   C₆-C₁₄ aryl such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl,        2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl,        3-phenanthryl, 4-phenanthryl and 9-phenanthryl, preferably        phenyl, 1-naphthyl and 2-naphthyl, with particular preference        phenyl,    -   silyl SiR¹⁰R¹¹R¹², where R¹⁰ to R¹² independently of one another        are selected from hydrogen, C₁-C₁₂ alkyl, C₇-C₁₅ aralkyl and        C₆-C₁₄ aryl; preference is given to the trimethylsilyl,        triethylsilyl, triisopropylsilyl, diethylisopropylsilyl,        dimethylhexylsilyl, tert-butyldimethylsilyl,        tert-butyldiphenylsilyl, tribenzylsilyl, triphenylsilyl and the        tri-para-xylylsilyl groups; particular preference is given to        the trimethylsilyl group and the tert-butyldimethylsilyl group;    -   siloxy OSiR¹⁰R¹¹R¹², where R¹⁰ to R¹² are selected independently        of one another from hydrogen, C₁-C₁₋₂ alkyl, C₇-C₁₅ aralkyl and        C₆-C₁₄ aryl; preference is given to the trimethylsilyloxy,        triethylsilyloxy, triisopropylsilyloxy,        diethylisopropylsilyloxy, dimethylthexylsilyloxy,        tert-butyldimethylsilyloxy, tert-butyldiphenylsilyloxy,        tribenzylsilyloxy, triphenylsilyloxy and the        tri-para-xylylsilyloxy groups; particular preference is given to        the trimethylsilyloxy group and the tert-butyldimethylsilyloxy        group;    -   C₁-C₁₂ alkoxy, preferably C₁-C₆ alkoxy such as methoxy, ethoxy,        n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy,        tert-butoxy, n-pentoxy, iso-pentoxy, n-hexoxy and iso-hexoxy,        with particular preference methoxy, ethoxy, n-propoxy and        n-butoxy;    -   C₆-C₁₄ aryl substituted in turn by one or more C₁-C₁₂ alkyl,        C₁-C₁₂ alkenyl, C₃-C₁₂ cycloalkyl, C₆-C₁₄ aryl, silyl        SiR¹⁰R¹¹R¹², siloxy OSiR¹⁰R¹¹R¹² or C₁-C₁₂ alkoxy groups        specified as above;    -   A¹ is O—R¹³, S—R¹³, N(R¹³)₂ or P(R¹³)₂, R¹³ being selected from        halogen, C₁-C₁₂ alkyl, C₂-C₁₂-alkenyl, C₃-C₁₂-cycloalkyl,        substituted or unsubstituted C₆-C₁₄ aryl groups or C₁-C₁₂ alkoxy        groups, these groups being as defined for R¹ to R⁶.

In one particular embodiment of the present invention, two adjacentradicals may together, with incorporation of the parent aromatic, form a5- to 10-membered ring. For example, in formula I a, R³ and R⁴ togethermay be: —(CH₂)₃— (trimethylene), —(CH₂)₄—(tetramethylene), —(CH₂)₅—(pentamethylene), —(CH₂)₆— (hexamethylene), —CH₂—CH═CH—,—CH₂—CH═CH—CH₂—, —CH═CH—CH═CH—, —O—CH₂—O—, —O—CH(CH₃)—O—,—O—CH—(C₆H₅)—O—, —O—CH₂—CH₂—O—, —O—C(CH₃)₂—O—, —NCH₃—CH₂—CH₂—NCH₃—,—NCH₃—CH₂—NCH₃— or —O—Si(CH₃)₂—O—.

In another embodiment of the present invention, compounds of the formulaI b are used as catalytically active components.

In formula I b, the variables are defined as follows:

Z¹ to Z⁴ independently of one another are

-   -   hydrogen,    -   halogen such as fluorine, chlorine, bromine or iodine,        preference being given to chlorine and bromine;    -   C₁-C₁₈ alkyl such as methyl, ethyl, n-propyl, iso-propyl,        n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl,        sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl,        iso-hexyl, sec-hexyl, n-heptyl, iso-heptyl, n-octyl, n-nonyl,        n-decyl, and n-dodecyl; preferably C₁-C₆ alkyl such as methyl,        ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl,        tert-butyl, n-pentyl, iso-pentyl, sec-pentyl, neo-pentyl,        1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl,        with particular preference C₁-C₄ alkyl such as methyl, ethyl,        n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and        tert-butyl,    -   C₁-C₁₂ alkyl substituted one or more times by donor atoms,        examples being noncyclic or cyclic ethers, alcohols, ketals,        thioethers or amines; specific examples are methoxymethyl,        ethoxymethyl, ethoxyethyl, β-hydroxyethyl, ω-ethoxypropyl,        (2-ethylhexyloxy)propylidene, methoxyethoxypropylidene or        ω-dimethylaminopropyl;    -   mono- or polyhalogenated C₁-C₁₂ alkyl groups such as        fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl,        dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl,        tribromomethyl, pentafluoroethyl, perfluoropropyl and        perfluorobutyl, with particular preference fluoromethyl,        difluoromethyl, trifluoromethyl and perfluorobutyl;    -   C₂-C₁₂ alkenyl, preferably C₂ to (O—C₈ alkenyl such as vinyl,        allyl, but-3-en-1-yl, ω-pentenyl, ω-hexenyl, ω-heptenyl, and        ω-octenyl;    -   C₃-C₁₂ cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl,        cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl,        cycloundecyl and cyclododecyl; preference is given to        cyclopentyl, cyclohexyl and cycloheptyl;    -   C₇ to C₂₀ aralkyl, preferably C₇ to C₁₂ phenylalkyl such as        benzyl, 1-phenethyl, 2-phenethyl, 1-phenylpropyl,        2-phenylpropyl, 3-phenylpropyl, 1-phenylbutyl, 2-phenylbutyl,        3-phenylbutyl and 4-phenylbutyl, with particular preference        benzyl,    -   C₆-C₁₄ aryl such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl,        2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl,        3-phenanthryl, 4-phenanthryl and 9-phenanthryl, preferably        phenyl, 1-naphthyl and 2-naphthyl, with particular preference        phenyl,    -   silyl SiR¹⁰R¹¹R¹², where R¹⁰ to R¹² independently of one another        are selected from hydrogen, C₁-C₁₂ alkyl, C₇-C₁₅ aralkyl and        C₆-C₁₄ aryl; preference is given to the trimethylsilyl,        triethylsilyl, triisopropylsilyl, diethylisopropylsilyl,        dimethylhexylsilyl, tert-butyldimethylsilyl,        tert-butyldiphenylsilyl, tribenzylsilyl, triphenylsilyl and the        tri-para-xylylsilyl groups; particular preference is given to        the trimethylsilyl group and the tert-butyldimethylsilyl group;    -   siloxy OSiR¹⁰R¹¹R¹², where R¹⁰ to R¹² independently of one        another are selected from hydrogen, C₁-C₁₂ alkyl, C₇-C₁₅ aralkyl        and C₆-C₁₄ aryl; preference is given to the trimethylsilyloxy,        triethylsilyloxy, triisopropylsilyloxy,        diethylisopropylsilyloxy, dimethylthexylsilyloxy,        tert-butyldimethylsilyloxy, tert-butyldiphenylsilyloxy,        tribenzylsilyloxy, triphenylsilyloxy and the        tri-para-xylylsilyloxy groups; particular preference is given to        the trimethylsilyloxy group and the tert-butyldimethylsilyloxy        group;    -   C₁-C₁₂ alkoxy, preferably C₁-C₆ alkoxy such as methoxy, ethoxy,        n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy,        tert-butoxy, n-pentoxy, iso-pentoxy, n-hexoxy and iso-hexoxy,        with particular preference methoxy, ethoxy, n-propoxy and        n-butoxy;    -   C₆-C₁₄ aryl, substituted in turn by one or more C₁-C₁₂ alkyl,        C₁-C₁₂ alkenyl, C₃-C₁₂ cycloalkyl, C₆-C₁₄ aryl, silyl        SiR¹⁰R¹¹R¹², siloxy OSiR¹⁰R¹¹R¹² or C₁-C₁₂ alkoxy groups        specified as above.    -   A² is selected from oxygen, sulfur, N-R¹³ and P-R¹³, preferably        N-R¹³ or P-R¹³, where R¹³ is as specified above.

In one particular embodiment of the present invention, two adjacentradicals may together with one another and including the parent aromaticform a 5- to 10-membered ring. Thus in formula I b, for example, R³ andR⁴ or Z¹ and Z² together may be: —(CH₂)₃— (trimethylene), —(CH₂)₄—(tetramethylene), —(CH₂)₅— (pentamethylene), —(CH₂)₆— (hexamethylene),—CH₂—CH═CH—, —CH₂—CH═CH—CH₂—, —CH═CH—CH═CH—, —O—CH₂—O—, —O—CH(CH₃)—O—,—O—CH—(C₆H₅)—O—, —O—CH₂—CH₂—O—, —O—C(CH₃) ₂—O—, —NCH₃CH₂—CH₂—NCH₃—,—NCH₃—CH₂—NCH₃— or —O—Si(CH₃)₂—O—.

In a further particular embodiment, Z⁴ and A may together with oneanother and including the phenyl ring in formula I b form a 5- to10-membered ring. In a preferred embodiment, Z⁴ and A form, withinclusion of the phenyl ring, an indol system.

The other variables R¹ to R⁴, M, X¹ and X² are as defined for formula Ia.

In formula I c

the variables are defined as follows:

X³, X⁴ and X⁵ independently of one another are

-   -   halogen such as fluorine, chlorine, bromine or iodine, chlorine        and bromine being particularly preferred;    -   trifluoroacetate,    -   BF₄ ⁻, PF₆ ⁻ or SbF₆ ⁻,    -   c₁-C₁₈ alkyl such as methyl, ethyl, n-propyl, iso-propyl,        n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl,        sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl,        iso-hexyl, sec-hexyl, n-heptyl, iso-heptyl, n-octyl, n-nonyl,        n-decyl, and n-dodecyl; preferably C₁-C₆ alkyl such as methyl,        ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl,        tert-butyl, n-pentyl, iso-pentyl, sec-pentyl, neo-pentyl,        1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl,        with particular preference C₁-C₄ alkyl such as methyl, ethyl,        n-propyl and n-butyl;    -   C₃-C₁₂ cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl,        cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl,        cycloundecyl and cyclododecyl; cyclopentyl, cyclohexyl and        cycloheptyl are preferred,    -   C₇ to C₂₀ aralkyl, preferably C₇ to C₁₂ phenylalkyl such as        benzyl, 1-phenethyl, 2-phenethyl, 1-phenylpropyl,        2-phenylpropyl, 3-phenylpropyl, 1-phenylbutyl, 2-phenylbutyl,        3-phenylbutyl and 4-phenylbutyl, with particular preference        benzyl,    -   C₆-C₁₄ aryl such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl,        2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl,        3-phenanthryl, 4-phenanthryl and 9-phenanthryl, preferably        phenyl, 1-naphthyl and 2-naphthyl, with particular preference        phenyl;    -   C₁-C₁₂ alkoxy, preferably C₁-C₆ alkoxy such as methoxy, ethoxy,        n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy,        tert-butoxy, n-pentoxy, iso-pentoxy, n-hexoxy and iso-hexoxy,        with particular preference methoxy, ethoxy, n-propoxy and        n-butoxy, or    -   NR⁸R⁹, where R⁸ and R⁹ independently of one another are selected        from hydrogen, C₁-C₁₂ alkyl, C₂-C₁₂ alkenyl and C₆-C₁₄ aryl,        which are able to form a saturated or unsaturated 5- to        10-membered ring; preference is given to the dimethylamino, the        diethylamino, the diisopropylamino, the methylphenylamino and        the diphenylamino groups. Examples of amino groups containing        saturated rings are the N-piperidyl group and the N-pyrrolidinyl        group; examples of amino groups containing unsaturated rings are        the N-pyrryl group, the N-indolyl group and the N-carbazolyl        group.

Preferably, X³ to X⁵ are identical; with very particular preference, X³to X⁵ are chlorine.

Nu¹ to Nu³ are selected independently of one another from N or P;preferably, Nu¹ and Nu² are each N, and with particular preference Nu¹to Nu³ are each N.

R¹⁴ to R¹⁶ independently of one another are

-   -   hydrogen,    -   halogen such as fluorine, chlorine, bromine or iodine,        preference being given to chlorine and bromine;    -   C₁-C₁₈ alkyl such as methyl, ethyl, n-propyl, iso-propyl,        n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl,        sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl,        iso-hexyl, sec-hexyl, n-heptyl, iso-heptyl, n-octyl, n-nonyl,        n-decyl, and n-dodecyl; preferably C₁-C₆ alkyl such as methyl,        ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl,        tert-butyl, n-pentyl, iso-pentyl, sec-pentyl, neo-pentyl,        1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl,        with particular preference C₁-C₄ alkyl such as methyl, ethyl,        n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and        tert-butyl,    -   C₁-C₁₂ alkyl substituted one or more times by donor atoms,        examples being noncyclic or cyclic ethers, alcohols, ketals,        thioethers or amines; specific examples are methoxymethyl,        ethoxymethyl, ethoxyethyl, β-hydroxyethyl, ω-ethoxypropyl,        (2-ethylhexyloxy)propylidene, methoxyethoxypropylidene or        ω-dimethylaminopropyl;    -   mono- or polyhalogenated C₁-C₁₂ alkyl groups such as        fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl,        dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl,        tribromomethyl, pentafluoroethyl, perfluoropropyl and        perfluorobutyl, particular preference being given to        fluoromethyl, difluoromethyl, trifluoromethyl and        perfluorobutyl;    -   C₂-C₁₂ alkenyl, preferably C₂ to ω-C₈ alkenyl such as vinyl,        allyl, but-3-en-1-yl, ω-pentenyl, ω-hexenyl, ω-heptenyl, and        ω-octenyl;    -   C₃-C₁₂ cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl,        cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl,        cycloundecyl and cyclododecyl; preference is given to        cyclopentyl, cyclohexyl and cycloheptyl;    -   C₇ to C₂₀ aralkyl, preferably C₇ to C₁₂ phenylalkyl such as        benzyl, 1-phenethyl, 2-phenethyl, 1-phenylpropyl,        2-phenylpropyl, 3-phenylpropyl, 1-phenylbutyl, 2-phenylbutyl,        3-phenylbutyl and 4-phenylbutyl, with particular preference        benzyl,    -   C₆-C₁₄ aryl such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl,        2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl,        3-phenanthryl, 4-phenanthryl and 9-phenanthryl, preferably        phenyl, 1-naphthyl and 2-naphthyl, with particular preference        phenyl,    -   silyl SiR¹⁰R¹¹R¹², where R¹⁰ to R¹² independently of one another        are selected from hydrogen, C₁-C₁₂ alkyl, C₇-C₁₅ aralkyl and        C₆-C₁₄ aryl; preference is given to the trimethylsilyl,        triethylsilyl, triisopropylsilyl, diethylisopropylsilyl,        dimethylhexylsilyl, tert-butyldimethylsilyl,        tert-butyldiphenylsilyl, tribenzylsilyl, triphenylsilyl and the        tri-para-xylylsilyl groups; particular preference is given to        the trimethylsilyl group and the tert-butyldimethylsilyl group;    -   siloxy OSiR¹⁰R¹¹R¹², where R¹⁰ to R¹² are selected independently        of one another from hydrogen, C₁-C₁₂ alkyl, C₇-C₁₅ aralkyl and        C₆-C₁₄ aryl; preference is given to the trimethylsilyloxy,        triethylsilyloxy, triisopropylsilyloxy,        diethylisopropylsilyloxy, dimethylthexylsilyloxy,        tert-butyldimethylsilyloxy, tert-butyldiphenylsilyloxy,        tribenzylsilyloxy, triphenylsilyloxy and the        tri-para-xylylsilyloxy groups; particular preference is given to        the trimethylsilyloxy group and the tert-butyldimethylsilyloxy        group;    -   C₁-C₁₂ alkoxy, preferably C₁-C₆ alkoxy such as methoxy, ethoxy,        n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy,        tert-butoxy, n-pentoxy, iso-pentoxy, n-hexoxy and iso-hexoxy,        with particular preference methoxy, ethoxy, n-propoxy and        n-butoxy;    -   C₆-C₁₄ aryl substituted in turn by one or more C₁-C₁₂ alkyl,        C₁-C₁₂ alkenyl, C₃-C₁₂ cycloalkyl, C₆-C₁₄ aryl, silyl        SiR¹⁰R¹¹R¹², siloxy OSiR¹⁰R¹¹R¹² or C₁-C₁₂ alkoxy groups        specified as above.

Preferably, R¹⁴ to R¹⁶ are identical.

R¹⁷ to R²² independently of one another are

-   -   hydrogen,    -   C₁-C₁₈ alkyl such as methyl, ethyl, n-propyl, iso-propyl,        n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl,        sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl,        iso-hexyl, sec-hexyl, n-heptyl, iso-heptyl, n-octyl, n-nonyl,        n-decyl, and n-dodecyl; preferably C₁-C₆ alkyl such as methyl,        ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl,        tert-butyl, n-pentyl, iso-pentyl, sec-pentyl, neo-pentyl,        1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl,        with particular preference C₁-C₄ alkyl such as methyl, ethyl,        n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and        tert-butyl,    -   mono- or polyhalogenated C₁-C₁₂ alkyl groups such as        fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl,        dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl,        tribromomethyl, pentafluoroethyl, perfluoropropyl and        perfluorobutyl, particular preference being given to        fluoromethyl, difluoromethyl, trifluoromethyl and        perfluorobutyl;    -   C₁-C₁₂ alkyl substituted one or more times by donor atoms,        examples being noncyclic or cyclic ethers, alcohols, ketals,        thioethers or amines; specific examples are methoxymethyl,        ethoxymethyl, ethoxyethyl, β-hydroxyethyl, ω-ethoxypropyl,        (2-ethylhexyloxy)propylidene, methoxyethoxypropylidene or        ω-dimethylaminopropyl;    -   C₂-C₁₂ alkenyl, preferably C₂ to ω-C₈ alkenyl such as vinyl,        allyl, but-3-en-1-yl, ω-pentenyl, ω-hexenyl, ω-heptenyl, and        ω-octenyl;    -   C₃-C₁₂ cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl,        cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl,        cycloundecyl and cyclododecyl; preference is given to        cyclopentyl, cyclohexyl and cycloheptyl;    -   C₇ to C₂₀ aralkyl, preferably C₇ to C₁₂ phenylalkyl such as        benzyl, 1-phenethyl, 2-phenethyl, 1-phenylpropyl,        2-phenylpropyl, 3-phenylpropyl, 1-phenylbutyl, 2-phenylbutyl,        3-phenylbutyl and 4-phenylbutyl, with particular preference        benzyl,    -   C₆-C₁₄ aryl such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl,        2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl,        3-phenanthryl, 4-phenanthryl and 9-phenanthryl, preferably        phenyl, 1-naphthyl and 2-naphthyl, with particular preference        phenyl,    -   silyl SiR¹⁰R¹¹R¹², where R¹⁰ to R¹² independently of one another        are selected from hydrogen, C₁-C₁₋₂ alkyl, C₇-C₁₅ aralkyl and        C₆-C₁₄ aryl; preference is given to the trimethylsilyl,        triethylsilyl, triisopropylsilyl, diethylisopropylsilyl,        dimethylhexylsilyl, tert-butyldimethylsilyl,        tert-butyldiphenylsilyl, tribenzylsilyl, triphenylsilyl and the        tri-para-xylylsilyl groups; particular preference is given to        the trimethylsilyl group and the tert-butyldimethylsilyl group;    -   siloxy OSiR¹⁰R¹¹R¹², where R¹⁰ to R¹² are selected independently        of one another from hydrogen, C₁-C₁₂ alkyl, C₇-C₁₅ aralkyl and        C₆-C₁₄ aryl; preference is given to the trimethylsilyloxy,        triethylsilyloxy, triisopropylsilyloxy,        diethylisopropylsilyloxy, dimethylthexylsilyloxy,        tert-butyldimethylsilyloxy, tert-butyldiphenylsilyloxy,        tribenzylsilyloxy, triphenylsilyloxy and the        tri-para-xylylsilyloxy groups; particular preference is given to        the trimethylsilyloxy group and the tert-butyldimethylsilyloxy        group;    -   C₁-C₁₂ alkoxy, preferably C₁-C₆ alkoxy such as methoxy, ethoxy,        n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy,        tert-butoxy, n-pentoxy, iso-pentoxy, n-hexoxy and iso-hexoxy,        with particular preference methoxy, ethoxy, n-propoxy and        n-butoxy;    -   C₆-C₁₄ aryl substituted in turn by one or more C₁-C₁₋₂ alkyl,        C₁-C₁₂ alkenyl, C₃-C₁₂ cycloalkyl, C₆-C₁₄ aryl, silyl        SiR¹⁰R¹¹R¹², siloxy OSiR¹⁰R¹¹R¹² or C₁-C₁₂ alkoxy groups        specified as above.

Preferably, R¹⁷, R¹⁹ and R²¹ are each identical, and preferably R¹⁸, R²⁰and R²² are each hydrogen. With very particular preference, R¹⁷ to R²²are hydrogen. The triazacyclohexane ligands necessary for synthesizingthese very particularly preferred compounds may be synthesized withparticular ease.

In one particular embodiment of the formula I c, two adjacent radicalsmay together form a saturated or unsaturated 4- to 9-membered ring; forexample, two radicals may together be: C₃-C₉ alkylidene such as, forexample, —(CH₂)₃— (trimethylene), —(CH₂)₄— (tetramethylene), —(CH₂)₅—(pentamethylene), —(CH₂)₆— (hexamethylene), —CH₂—CH═CH—,—CH₂—CH═CH—CH₂—, —CH═CH—CH═CH—; and also cyclic aldols, ketals or aminessuch as, for example, —O—CH₂—O—, —O—CH(CH₃)—O—, —O—CH—(C₆H₅)—O—,—O—CH₂—CH₂—O—, —O—C(CH₃)₂—O—, —N(CH₃)—CH₂—CH₂—N(CH₃)—,—N(CH₃)—CH₂—N(CH₃)—or —O—Si(CH₃)₂—O—.

The other variables are as defined for formula I a.

In a further embodiment, the polyolefin wax is prepared by catalysiswith a single-site catalyst based on a tri-pnicogen-cyclohexane complexof the formula Ic.

In a further embodiment, the polyolefin wax is prepared by catalysiswith a single-site catalyst based on a 1,3,5-triazacyclohexane complex,a 1,3-diaza-5-phosphacyclohexane complex or a 1,3,5-triphospacyclohexanecomplex of the formula Ic.

The preparation of the transition metal complexes of the formula I a toc is known per se. Suitable syntheses for complexes of the formula I aand b can be found in DE-A 197 10 615, in A. Döhring et al.,Organometallics 2000, 19, 388, and also in J. C. Weber, Dissertation,MPI Mulhouse/Ruhr, 1999.

The preparation of the particularly preferred triazacycloalkane ligandsfor complexes of the formula I c is known per se. Those for thesynthesis of the very particularly preferred compounds of the formula Ic where R¹⁷ to R²² are each hydrogen and the radicals R¹⁴ to R¹⁶ areeach identical may be synthesized very effectively by mixingformaldehyde in the form, for example, of formalin solution with theassociated amine R¹⁴—NH₂. Various synthesis pathways for these complexligands are described, for example, in F. Weitl et al., J. Am. Chem.Soc. 1979, 101 2728; M. Takahashi, S. Takamoto, Bull. Chem. Soc. Japan1977, 50, 3413; T. Arishima et al., Nippon Kagaku Kaishi 1973, 1119; L.Christiansen et al. Inorg. Chem. 1986, 25, 2813; L. R. Gahan et al.,Aust. J. Chem. 1982, 35, 1119; B. A. Sayer et al., Inorg. Chim. Acta,1983, 77, L63; K Wieghardt et al., Z. Naturforsch., 1983, 38b, 81 and I.A. Fallis et al., J. Chem. Soc., Chem. Commun. 1998, 665.

The metal complexes, especially the chromium complexes, may be obtainedin a simple manner by reacting the corresponding metal salts such asmetal chlorides or metal carbonyls, for example, with the ligands, asfor example in P. Chaudhuri, K. Wieghardt, Prog. Inorg. Chem. 1987, 35,329 or G. P. Stahley et al., Acta Crystall. 1995, C51, 18.

In order that above complexes of the formulae I a to c are catalyticallyactive, they are activated with a cation-forming compound. Suitablecation-forming compounds are selected aluminum or boron compounds havingelectron withdrawing radicals (e.g. trispentafluorophenylborane,trispentafluorophenylaluminum, N,N-dimethylaniliniumtetrakispentafluorophenylborate, tri-n-butylammoniumtetrakispentafluorophenylborate, N,N-dimethylaniliniumtetrakis(3,5-bisperfluoromethyl)phenylborate, tri-n-butylammoniumtetrakis(3,5-bisperfluoromethyl)phenylborate, and trityliumtetrakispentafluorophenylborate). These activators for complexes of theformulae I a to c are described in DE-A 199 35 407, in PCT/EP 0002716,and in Angew. Chem. Int. Ed., 1994, Vol. 33, p. 1877. Preference isgiven to dimethylanilinium tetrakispentafluorophenylborate, trityliumtetrakispentafluorophenylborate, and trispentafluorophenylborane.

Where boron or aluminum compounds are used as activators for thecomplexes of the formulae I a to c, they are generally employed in amolar ratio of from 1:10 to 10:1, based on M; preferably from 1:2 to 5:1and with particular preference from 1:1.5 to 1.5:1.

Another suitable class of cation-forming compounds comprises thealuminoxanes of the formulae II a and b.

The structure of the aluminoxanes is not precisely known. They areproducts obtained by careful partial hydrolysis of aluminum alkyls (seeDE-A 30 07 725). These products do not exist in pure form but areinstead mixtures of open-chain and cyclic structures of type II a and b.These mixtures are presumed to exist in a dynamic equilibrium with oneanother.

In formulae II a and b, the radicals R²³ independently of one anotherare

-   -   C₁-C₁₂ alkyl such as methyl, ethyl, n-propyl, iso-propyl,        n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl,        sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl,        iso-hexyl, sec-hexyl, n-heptyl, iso-heptyl, n-octyl, n-nonyl,        n-decyl, and n-dodecyl; preferably C₁-C₆ alkyl such as methyl,        ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl,        tert-butyl, n-pentyl, iso-pentyl, sec-pentyl, neo-pentyl,        1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl;        methyl is particularly preferred;    -   C₃-C₁₂ cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl,        cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl,        cycloundecyl and cyclododecyl; preference is given to        cyclopentyl, cyclohexyl and cycloheptyl;    -   C₇ to C₂₀ aralkyl, preferably C₇ to C₁₂ phenylalkyl such as        benzyl, 1-phenethyl, 2-phenethyl, 1-phenylpropyl,        2-phenylpropyl, 3-phenylpropyl, 1-phenylbutyl, 2-phenylbutyl,        3-phenylbutyl and 4-phenylbutyl, with particular preference        benzyl, or    -   C₆-C₁₄ aryl such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl,        2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl,        3-phenanthryl, 4-phenanthryl and 9-phenanthryl, preferably        phenyl, 1-naphthyl and 2-naphthyl, with particular preference        phenyl; and    -   n is an integer from 0 to 40, preferably from 1 to 25, and with        particular preference from 2 to 22.

In the literature, cagelike structures are also discussed foraluminoxanes (Y. Koide, S. G. Bott, A. R. Barron Organometallics 1996,15, 2213-26; A. R. Barron Macromol. Symp. 1995, 97, 15-25).

Irrespective of the actual structure of the aluminoxanes, they aresuitable activators for complexes of transition metals of the formulae Ia to c.

Mixtures of different aluminoxanes are particularly preferred activatorsin those cases where polymerization is conducted in a solution of aparaffin, n-heptane or isododecane, for example. One particularlypreferred mixture is the CoMAO available commercially from Witco GmbH,having a formula of [(CH₃)_(0.9)(iso-C₄H₉)_(0.1)AlO]_(n).

To activate the complexes of the formula I a to c with aluminoxanes, itis generally necessary to use an excess of aluminoxane, based on M.Sensible M:Al molar ratios are situated within the range from 1:10 to1:10 000, preferably from 1:50 to 1:1000, and with particular preferencefrom 1:100 to 1:500.

The chosen complex of the formulae I a to c and the cation-formingcompound together form a catalyst system. By adding one or more furtheraluminum alkyl compounds of the formula Al(R²³)₃ it is possible toincrease further the activity of this catalyst system.

By adding further aluminum alkyl of the formula Al(R²³)₃ or aluminoxanesit is possible to increase the activity of the catalyst system; aluminumalkyls of the formula Al(R²³)₃ or aluminoxanes may also act as molecularmass regulators. Another effective molecular mass regulator is hydrogen.The molecular mass may be regulated with particular effect by thereaction temperature and the residence time.

Modern large-scale industrial preparation processes for polyolefin waxesare solution processes, suspension processes, bulk polymerizationprocesses in liquid or supercritical monomer, and gas phase processes,the latter being either stirred gas phase or gas-phase fluidized bedprocesses.

In order that the complexes of the formulae I a to c may be used insuspension processes, bulk polymerization processes or gas phaseprocesses, it is advantageous to immobilize them on a solid support.Otherwise, morphological problems of the polymer (crumbs, wall deposits,blockages in pipes or heat exchangers) may occur, forcing shutdown ofthe plant.

Catalyst systems comprising complexes of the formulae I a to c andactivator may be effectively deposited on a solid support. Examples ofsuitable support materials are porous metal oxides, of metals fromgroups 2-14 or mixtures thereof, and also sheet silicates, and alsosolid halides of metals from groups 1, 2 and 13, and polymers such as,for example, polyethylene or polypropylene. Preferred examples of metaloxides from groups 2-14 are SiO₂, B₂O₃, Al₂O₃, MgO, CaO and ZnO.Preferred sheet silicates are montmorillonites or bentonites; preferredhalides are MgCl₂ or amorphous AlF₃.

Particularly preferred support materials are spherical silica gels andalumosilicate gels of the formula SiO₂.a Al₂O₃, where a is generally anumber in the range from 0 to 2, preferably from 0 to 0.5. Silica gelsof this kind are available commercially, e.g., Silica Gel 332, Sylopol®948 or Sylopol 952 or S 2101 from W. R. Grace or ES 70×from Crosfield.

Proven particle sizes for the support material comprise average particlediameters of 1-300 μm, preferably from 20 to 80 μm, the particlediameter being determined by means of known methods such as sievemethods. The pore volume of these supports is from 1.0 to 3.0 ml/g,preferably from 1.6 to 2.2 ml/g, and with particular preference from 1.7to 1.9 ml/g. The BET surface area is from 200 to 750 m²/g, preferablyfrom 250 to 400 m²/g.

In order to remove impurities, especially moisture, adhering to thesupport material, the support materials may be heated out prior todoping, suitable temperatures being from 45 to 1000° C. Temperatures offrom 100 to 750° C. are particularly suitable for silica gels and othermetal oxides; for MgCl₂ supports, temperature ranges from 50 to 100° C.are preferred. This heating out should take place over a period of from0.5 to 24 hours, heatout times of from 1 to 12 hours being preferred.The pressure conditions are not critical per se; heating out may takeplace under atmospheric pressure. Advantageously, however, use is madeof reduced pressures of from 0.1 to 500 mbar; a particularlyadvantageous range is from 1 to 100 mbar and a very particularlyadvantageous range from 2 to 20 mbar. Chemical pretreatment of thesupport material is another possibility.

The general procedure for doping the catalyst is to slurry the supportmaterial in a suspension medium and to combine this suspension with thesolution of a complex of the formula I a to c and of the activator. Thevolume of the suspension medium is from 1 to 20 times the pore volume ofthe catalyst support. Subsequently, the catalyst may be separated fromthe suspension medium by means of an appropriate method, such asfiltration, centrifugation or evaporation.

For better control of the morphology, the catalyst may be prepolymerizedwith small amounts of monomer prior to the polymerization proper. Theprepolymerization can be terminated by adding a reversible catalystpoison or by ending the feed of monomer, and the prepolymerized catalystmay subsequently be added to the polymerization unit.

Suitable monomers include the following olefins: ethylene, propylene,1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene or 1-undecene,ethylene being particularly preferred.

Suitable comonomers include α-olefins, such as from 0.1 to 20 mol % of1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene or1-undecene. Isobutene, however, is also a suitable comonomer.

In order to prevent the electrostatic charging of the polymerizationunit or of the product that is occasionally observed withpolymerizations, an antistat may be added to the reaction mixture.Suitable antistats are dilute solutions of aliphatic alcohols, such asisopropanol, in paraffins such as n-heptane, for example. Furthersuitable antistats are available commercially as Stadis® products fromDuPont.

In order to prepare the paints and printing inks of the invention, thewax, which in large-scale industrial plants is usually obtained in theform of a coarse powder, is micronized in a subsequent step.Micronization is carried out using mills, an example being air jetmills. As a result of micronization, the wax is obtained as what isknown as micropowder, the maximum particle diameter not exceeding 30 μmand preferably not exceeding 25 μm.

The conventional principal constituents of the paint or printing ink ofthe invention, in the amounts prescribed by the formulation, are firstof all mixed with the micronized wax in high-speed stirrers known asdissolvers. Subsequently they are mixed further, for example, in stirredball mills with a friction gap, which have been charged with grindingbeads having a diameter of from 0.05 to 5 mm, preferably from 0.5 to 2.5mm, and with particular preference 2 mm. Thereafter, the paint or ink ofthe invention is passed optionally through a triple-roll mill in orderto remove the oxygen incorporated by stirring. Alternatively, theprinting ink may also be degassed by application of a vacuum.

The weight fraction of the wax in the printing inks and paints of theinvention is from 0.05 to 65% by weight, preferably from 0.1 to 10% byweight, and with particular preference from 0.5 to 3% by weight. Theweight fraction of the wax in the copier toners of the invention is, forexample, from 45 to 65% by weight.

Further components of the printing inks of the invention are from 5 to30% by weight of an organic or inorganic pigment, organic pigments beingpreferred; and also from 65 to 90% by weight of binder, comprising aresin and, optionally, one or more solvents such as ethanol, methanol,isopropanol, water, toluene or low molecular mass hydrocarbons, forexample, and also optionally oils and antioxidants.

The printing inks of the invention are notable for particular mechanicalstability, especially abrasion resistance, and for particular gloss. Theprinting inks are therefore suitable to be employed for pinting on paperor cardboard.

WORKING EXAMPLE

Preparation of the complex (n-C₁₂H₂₅NCH₂)₃CrCl₃ and polymerization ofethylene are described fundamentally in DE-A 199 35 407, in PCT/EP0002716, and in Angew. Chem. Int. Ed. 1994, Vol. 33, p. 1877. Thepreparation of offset printing inks is described, for example, in theproduct brochure “Luwax® Poligen® Waxes and Dispersions—Use in PrintingInks”, fundamentally, dating from 1992.

The scuff resistance was determined in a Prufbau-Quartant scuff tester,while for measuring the gloss a multiangle reflectometer “Multigloss”from Byk-Chemie was used.

In a 10 liter steel autoclave (from Buchi), 50 mg (67 mmol) of(n-C₁₂H₂₅NCH₂)₃CrCl₃, dissolved in toluene, were activated with 14 ml of30% MAO from Witco, the Al:Cr ratio set being 1000:1. 4 l of isobutaneand 80 l (3.8 mol) of hydrogen were injected, and the autoclave was thenheated to 90° C. Subsequently, 40 bar of ethylene were injected andpolymerization was conducted for 30 minutes, the pressure beingmaintained at 40 bar by adding further ethylene.

The polymerization was terminated by letting down the autoclave.

Yield: 460 g, corresponding to an activity of 14,000 kg of PE(mol Cr·h).

The wax thus obtained had the following properties: melting point 128.5°C.; M_(w): 5200 g, M_(n): 2100 g. M_(w)/M_(n)=2.5.

Number of vinyl and vinylidene double bonds/1000 carbon atoms: from 0.5to 2.3.

The wax was micronized in an opposed-jet mill until it had a diameter of9 μm (median), determined by laser diffraction using a Coulter counter.

Example 1

1.0% by weight of wax was dispersed in a hydrocarbon (toluene) and thenincorporated into an offset printing ink Novaboard cyan 4 C 86 from K+EDruckfarben (wax-free), comprising 18% by weight organic pigment, 31% byweight rosin, 34% by weight glue resin and 16% by weight mineral oil.

For the comparative examples, the following waxes were incorporatedanalogously into the offset printing ink and tested.

-   V1: Luwax® AF 30, BASF Aktiengesellschaft, prepared by high-pressure    polymerization-   V2: Clariant Wachs PE 520® prepared by Ziegler-Natta catalysis-   V3: Polyethylene wax, prepared by metallocene catalysis in    accordance with EP-A 0 890 619, example 3

For testing the abrasion resistance, a sample print was made using amultipurpose test bed printing machine from Dr. Dürner on paper of typePhoenomatt 115 g/m² (Scheufelen GmbH & Co. KG). The scuffing behaviorwas investigated on a scuffing tester from Scheuerprüfer PrüfbauQuartett), setting a scuffing load of 48 g/cm² and a scuffing speed of15 cm/s. Assessment was made of the intensity of the color transferredto the test sheet through a determination of the color difference inaccordance with DIN 6174, a relatively low color difference valueindicating advantageous properties.

TABLE 1 Results Color difference after Particle diameter Experiment 200strokes d₅₀ [μm] 1 1.9 8.9 V1 3.9 8.7 V2 3.2 9.1 V3 2.2 9.0 No wax 15.9—

1. A printing ink or paint comprising a polyolefin wax componentprepared from one or more olefins by catalysis with a single-sitecatalyst based on a complex of the formulae Ia to Ic,

where the variable are defined as follows: M is an element selected fromthe group consisting of V, Nb, Ta, Cr, Mo, W, Mn and Fe in oxidationstate +3; X¹ to X⁵ are selected from a group consisting of halogen,trifluoroacetate, BF₄ ⁻, PF₆ ⁻or SbF₆ ⁻, C₁-C₁₈ alkyl, C₃-C₁₂cycloalkyl, C₇-C₂₀ aralkyl, C₆-C₁₄ aryl, C₁-C₁₂ alkoxy and NR⁸R⁹; R⁸ andR⁹ are, independently of one another, hydrogen, C₁-C₁₂ alkyl, C₂-C₁₂alkenyl or C₆-C₁₄ aryl, or form, together with the nitrogen to whichthey are bonded, a saturated or unsaturated 5- to 10-membered ring; R¹to R⁶, and Z¹ to Z⁴, are independently of one another selected from agroup consisting of: hydrogen; halogen; C₁-C₁₈ alkyl; C₁-C₁₂ alkyl;substituted one or more times by donor atoms; mono- or polyhalogenatedC₁-C₁₂ alkyl groups; C₂-C₁₂ alkenyl; C₃-C₁₂ cycloalkyl; C₇-C₂₀ aralkyl;C₆-C₁₄ aryl; silyl SiR¹⁰R¹¹ ¹²; siloxy OSiR¹⁰R¹¹R¹²; C₁-C₁₂ alkoxy; andC₆-C₁₄ aryl which is in turn substituted by one or more C₁-C₁₂ alkyl,C₁-C₁₂ alkenyl, C₃-C₁₂ cycloalkyl, C₆-C₁₄ aryl, silyl SiR¹⁰R¹¹R¹²,siloxy OSiR¹⁰R¹¹R¹² or C₁-C₁₂ alkoxy groups; and, in formulae Ia and Ib,two adjacent radicals R¹ to R⁶, Z¹ to Z⁴, R¹⁴ to R¹⁶ together with thering to which they are bonded, may form a 5- to 10-membered ring; R¹⁷ toR²² are independently of one another selected from a group consistingof: hydrogen; C₁-C₁₈ alkyl; C₁-C₁₂ alkyl substituted one or more timesby donor atoms; mono- or polyhalogenated C₁-C₁₂ alkyl groups; C₂-C₁₂alkenyl; C₃-C₁₂ cycloalkyl; C₇-C₂₀ arakyl; C₆-C₁₄ aryl; silylSiR¹⁰R¹¹R¹²; siloxy OSiR¹⁰R¹¹R¹²; C₁-C₁₂ alkoxy; and C₆-C₁₄ aryl whichis in turn substituted by one or more C₁-C₁₂ alkyl, C₁-C₁₂ alkenyl,C₃-C₁₂ cycloalkyl, C₆-C₁₄ aryl, silyl SiR¹⁰R¹¹R¹², siloxy OSiR¹⁰R¹¹R¹²or C₁-C₁₂ alkoxy groups; and, in formula Ic, two adjacent radicals R¹⁴to R²² may together form a saturated or unsaturated 4- to 9-memberedring; R¹⁰ to R¹² are independently of one another hydrogen, C₁-C₁₂alkyl, C₇-C₁₅ aralkyl or C₆-C₁₄ aryl; A¹ is O—R¹³, S—R¹³, N—(R¹³)₂ orP—(R¹³)₂; A² is oxygen, sulfur, N—R¹³ or P—R¹³; and, in formula Ib, Z⁴and A² together with the phenyl ring to which they are bonded, may forma 5- to 10-membered ring; R¹³ is halogen, C₁-C₁₂ alkyl which isoptionally mono- or polysubstituted with donor atoms, mono- orpolyhalogenated C₁-C₁₂ alkyl, C₃-C₁₂ cycloalkyl, C₁-C₁₂ alkoxy, orC₆-C₁₄ aryl which is optionally substituted by one or more C₁-C₁₂ alkyl,C₁-C₁₂ alkenyl, C₃-C₁₂ cycloalkyl, C₆-C₁₄ aryl, silyl SiR¹⁰R¹¹R¹²,siloxy OSiR¹⁰R¹¹R¹² or C₁-C₁₂ alkoxy groups; Nu¹ to Nu³ are each N or P.2. A printing ink or paint as claimed in claim 1, wherein the polyolefinwax is prepared by catalysis with a single-site catalyst based on atri-pnicogen-cyclohexane complex of the formula Ic.
 3. A printing ink orpaint as claimed in claim 1, wherein the polyolefin wax is prepared bycatalysis with a single-site catalyst based on a 1,3,5-triazacyclohexanecomplex, a 1,3-diaza-5-phosphacyclohexane complex or a1,3,5-triphosphacyclohexane complex of formula Ic.
 4. A printing ink orpaint as claimed in claim 1, wherein the polyolefin wax is prepared bycatalysis with a single-site catalyst based on a Cr complex of theformula Ic.
 5. A process for preparing the printing ink or paint definedin claim 1, which comprises adding micronized particles of thepolyolefin wax component to a printing ink or paint.
 6. A method ofprinting paper or cardboard, which comprises applying the printing inkin claim 1 to the paper or the cardboard.
 7. The printing ink or paintdefined in claim 1, wherein the polyolefin component is a polyethylenecomponent.
 8. The printing ink or paint defined in claim 1, wherein thepolyolefin component is a homopolymer or is a copolymer of an olefin andfrom 0.1 to 20 mol-% of one or more comonomers selected from the groupconsisting of 1-butene, isobutene, 1-pentene, 1-hexene,4-methyl-1-pentene, 1-octene, 1-decene and 1-undecene.